SK7462002A3 - Bridged metallocene compounds as olefin-polymerization catalysts - Google Patents

Abstract

The present invention relates to metallocene compounds consisting of indenyl-cyclopentadienyl groups non-symmetrically joined by a bivalent radical. Said compounds can be conveniently used as components of catalysts for the polymerization of olefins.

Description

Bridged metallocene compounds as olefin polymerization catalysts

Technical field

The invention relates to bridged metallocene compounds, corresponding ligands, to a process for their preparation and to the use of said compounds as catalyst components for olefin polymerization.

More particularly, the invention relates to metallocene compounds consisting of indenylcyclopentadienyl groups, asymmetrically bound by a divalent radical.

BACKGROUND OF THE INVENTION

It is known that metallocene compounds can be used in a wide variety of industrially interesting reactions.

For example, chiral, stereospecifically rigid metallocene compounds consisting of two bridged indenyl groups and a metal, such as zirconium, are known to be used as catalyst constituents for olefin polymerization, and in particular in the preparation of stereo-regular polyolefins.

In these metallocene compounds, the indenyl groups are linked via bivalent radicals having two or more carbon atoms, for example, by - (CH ₂ ) 2 groups, or other atoms such as carbon atoms.

These radicals are generally attached to the ring of 5 carbon atoms of both indenyl groups at different positions, as disclosed, for example, in patent applications EP-A-485 823,

EP-A-372,414 and WO 94/11406.

Also known are metallocene groups whose indenyl groups are linked via divalent radicals attached at the 4-position on the 6-carbon ring of both indenyl groups, see, for example, patent applications EP 693 502 and WO 96/38458.

We have now found novel metallocene compounds in which the divalent radical is bonded to the 5-carbon ring of the cyclopentadienyl, indenyl or fluorenyl group and to the 6-carbon ring of the indenyl group and which can be conventionally used as catalyst components for olefin polymerization.

SUMMARY OF THE INVENTION

In particular, the invention provides metallocene compounds of the formula I:

where :

R 1 and R ₂ may be in any free positions

R 1, indene;

R 2, R ₃ , R ₄ , R 5, R 7 and R 8 are halogen, bromine, preferably linear unsaturated hydrocarbyl hydrocarbyl substituted independently represent hydrogen, fluorine, chlorine or a 1-membered or branched-chain cycloaliphatic group saturated or aromatic or in and from carbon atoms or carbon atoms with multiple halogen atoms, or a hydrocarbyl group having 1 to 20 carbon atoms containing one or more heteroatoms selected from groups 14 to 16 of the Periodic Table of the Elements, preferably oxygen, nitrogen, in addition any two of the silicon atom, the sulfur atom, and the substituent substituents adjacent, are phosphorus;

Rs.

R ₃ , r ₄ , to each other

R5 a

Rs a

R ₆ or both

R ₆ , which are bonded such that or an unsaturated cyclic carbon structure wherein more together form two pairs saturated with each other by up to 20 cyclopentadienyl ring atoms optionally contains one or more of the specified heteroatoms;

comprising a bond said structure being a metal atom selected from the group consisting of titanium, zirconium or hafnium;

X 1 and X ₂ each independently represent an anionic group attached to the metal atom M.

Typical examples of Χχ and X ₂ are hydride, halide, preferably chloride, linear or branched alkyl such as methyl, ethyl, butyl, isopropyl, isoamyl, octyl, decyl, benzyl, allyl, methylallyl, and cycloalkyl such as cyclopentyl, cyclohexyl, 4-methylcyclohexyl, aryl, such as phenyl or toluyl, alkoxy or thioalkoxy, such as methoxy, ethoxy or isobutoxy an ethylsulfide group and a carboxyl group such as acetate, propionate, butyrate, pivalate, versatate, naphthenate or again, a dialkylamide group such as a diethylamide group, a dibutylamide group or an alkylsilylamide group such as bis (trimethylsilyl) amides group.

X 1 and X ₂ can also be chemically bonded to each other to form a ring having 4 to 7 atoms other than hydrogen, and the ring also contains a metal M atom.

Typical examples of this aspect are divalent anionic groups such as trimethylene or tetramethylene or ethylenedioxy.

The metallocene compounds of the invention may exist in isomeric, racemic or mesomeric forms.

The invention also relates to compounds of formula Ia which are useful for the preparation of compounds of formula I:

* 5 "Rj A r ₂ ^ a, where: R1 / R2 / R3! R4! R 5, R 6, R; and Re have as defined above

Examples of structures of the compounds of formula Ia are shown in Table 1 below:

wherein Me is methyl; and

Ph is phenyl

Table 1: Examples of structures of compounds of formula Ia

Compounds of formula (Ia) can be prepared by a simple and original method, which schematically illustrates Reaction Scheme 1 below.

Reaction scheme 1

D

a = LiBu (2 equiv.) / hexane; b = diethyl carbonate;

c = PTSA / toluene; d = LiAlH ₄ or LiR or RMgX; e = PBr; f = Li (C ₅ HR ₃ R ₄ R ₅ R 6)

The method includes the following steps:

(a) contacting 1-indanol derivatives of the formula II wherein the substituents R, _X and _R2 are as defined above, with LiBu to give the double salt of formula III;

(b) reacting the lithium double salt of formula III obtained in step (a) with electrophilic reagents such as diethyl carbonate to form a hydroxyester of formula IV;

(c) conducting a dehydration reaction of the alcohol function of the hydroxy ester of formula IV obtained in step (b) in an acid medium to form an ester of formula V;

(d) conducting a reduction reaction of the ester of formula V obtained in step (c) to give an alcohol of formula VI;

(e) performing a bromination reaction of an alcohol of Formula VI to form a bromine derivative of Formula VII;

(f) forming an indenyl derivative of formula (Ia) using the bromine derivative of formula (VII) obtained in step (e) and the lithium salts of cyclopentadienyl anions whose corresponding neutral derivative can be expressed as starting material.

using formula VIII:

VIII in which R ₃ , R ₄ ,

R ₅ and R _{6 are} as defined above.

Step (a) of the process of the invention is described in Chem. Ber.

(1980) 113, 1304.

This article essentially informs that some benzyl alcohols and other phenylcarbinols, including but not limited to 1-indanol (Synthesis (1981) 59), can be deprotonated in the presence of butyllithium and tetramethylenediamine in pentane to form lithium (ortho lithium) alkoxides.

The reaction described in step (a) can be carried out: in the presence of basic reagents such as butyllithium, methyllithium and sodium hydride in hydrocarbon and / or ether solvents or mixtures thereof at temperatures of -30 ° C to +120 ° C; preferred conditions include the use of butyllithium in hexane at temperatures of 0 ° C to + 70 ° C.

Typical 1-indanols of formula II are 1-indanol, 2-methyl-1-indanol, 3-methyl-1-indanol, 3-ethyl-1-indanol and 4-methyl-1-indanol.

One advantage of the process of the invention is that many 1-indanol derivatives are commercially available or can be readily prepared by art-known acylation / alkylation reactions of appropriately substituted aromatic rings.

Step (b) of the process of the invention comprises reacting the lithium double salt of formula III with electrophilic reagents, with diethyl carbonate, dimethyl carbonate, carbon dioxide and ethyl chloroformate in hydrocarbon and / or ether solvents or mixtures thereof at -100 ° C being particularly suitable for this purpose. C to +120 ° C, preferably with diethyl carbonate in hexane at temperatures of -70 ° C to +25 ° C.

Step (c) of the process of the invention consists in dehydrating the hydroxy ester of formula IV and obtaining the corresponding indenyl derivative of formula V.

This reaction can be carried out in the presence of strong acids such as hydrochloric acid, sulfuric acid, paratoluenesulfonic acid or milder dehydrating agents, for example in the presence of silica gel.

The choice of solvent for this reaction is very broad, since non-polar solvents such as aliphatic hydrocarbons, medium polar solvents such as aromatic hydrocarbons, or polar solvents such as ethers or chlorinated hydrocarbons can be successfully used; the temperature at which the reaction can take place can also be chosen from a wide range, generally from + 25 ° C to +150 ° C, the choice being generally not only dependent on the substrate but also on the type of solvent used, preferably paratoluenesulfonic acid in the toluene at temperatures ranging from +50 to + 110 ° C.

Step (d) of the process of the invention comprises reducing the ester group to an alcohol to form a compound of Formula VI; this reduction can be carried out using a variety of reagents, including, for example, LiAlH ₄ , NaBH ₄ , NaH, MgH ₂ , LiBu, LiMe, MeMgCl, PhMgBr, ButMgCl, usually in ether solvents, but alternative solvents can also be used having other characteristics, at temperatures ranging from -70 ° C to + 100 ° C; LiAl ₄ in ethyl ether is preferably used at temperatures ranging from -30 ° C to +25 ° C.

Step (e) of the process of the invention comprises brominating an alcohol functionality to form a bromo derivative of Formula VII; again, there are various synthetic alternatives known to those skilled in the art and include the use of a wide variety of different brominating agents in different solvents; preferred conditions include the use of PBr ₃ in methylene chloride at temperatures ranging from -20 ° C to +25 ° C.

Step (f) of the process of the invention comprises reacting the cyclopentadienyl anion with a bromine derivative of formula VII, which is obtained by reacting the corresponding neutral derivative of formula VIII with a suitable base.

Those skilled in the art are familiar with the wide variety of products capable of meeting this requirement; in fact, alkyls or hydrides of electropositive metals such as methyl lithium, butyl lithium, tert-butyl lithium, dibutyl magnesium, sodium hydride, potassium hydride, magnesium hydride, known Grignard reagents: RMgX, as well as alkali metals or alkali metals themselves may be used or their alloys.

As a rule, all reagents are readily available on the market at affordable prices, and thus the choice of a particular reagent will generally depend on the type of substrate to be anion. obtained.

Solvents for carrying out this reaction may be selected from aliphatic or aromatic hydrocarbons, ethers and / or mixtures thereof, the preferences of one or the other often depending on the particular solubility or reaction rate requirements.

_f J

The temperatures at which the reaction is carried out may vary within a very wide range, generally from -80 ° C to +110 ° C, and are essentially dependent on the thermal stability of the substrates and the solvent used.

Preferred conditions for obtaining anions of the compound of formula VIII include the use of butyllithium in a mixture of hexane and THF at temperatures ranging from ° C to +60 ° C.

Typical compounds of Formula VIII are: cyclopentadiene, methylcyclopentadiene, tetramethylcyclopentadiene, trimethylsilylcyclopentadiene, indene, 3-methylindene, 4,7-dimethylindene, 5,6-dimethylindene, 4,5,6,7-tetrahydroindene,

4,5,6,7-tetrahydro-2-methylindene, 2,4,5,6,7,8-hexahydroazulene,

2-Methyl-2,4,5,6,7,8-hexahydroazulene

4,5,6,7,8,9-hexahydro-2H-cyclopentacyclooctene, 4,5,6,7,8,9,10,11,12,13-decahydro-2H-cyclopentacyclododecene, fluorene and 1,2, 3,4,5,6,7,8-octahydrofluorenes.

In a preferred embodiment, the compound of formula VIII is cyclopentadiene, tetramethylcyclopentadiene, indene,

3-methylindene, 4,7-dimethylindene, 2,4,5,6,7,8-hexahydro-azulene, fluorene.

In an even more preferred embodiment, the compound of formula VIII is indene and 4,7-dimethylindene.

This reaction may be carried out in a wide variety of solvents, which may be selected from aromatic and / or aliphatic hydrocarbons and ethers and / or mixtures thereof, at a temperature ranging from -80 ° C to +120 ° C. no particular limitation on the order of addition of the individual reagents is preferred if the bromine derivative of formula VII, either pure or diluted in an ether solvent, is added to the solution or suspension containing the cyclopentadienyl anion obtained as described above, at temperatures , which range from -70 ° C to +25 ° C.

Alternatively, step (f) of the process of the invention can be carried out by reacting the brominated product of formula (VII) with a suitable lithium enolate, resulting in the indenylcyclopentadienyl products of formula (XIII):

XIII, where:

R 1 and R ₂ independently of each other may occupy any free position of the indene group;

R _x, R _2, R 7, R, R, R and R _{X 1} each independently represent hydrogen, halogen, preferably F, Cl or Br, a linear or branched hydrocarbyl radical having 1 to 20 carbon atoms, saturated or unsaturated, cycloaliphatic or an aromatic or hydrocarbyl group having 1 to 20 carbon atoms substituted by one or more substituents selected from the group consisting of a halogen atom or a hydrocarbyl group having 1 to 20 carbon atoms containing one or more heteroatoms from Group 14 to 16 of the Periodic Table, preferably from a silicon atom, an oxygen atom, l

a nitrogen atom, a sulfur atom, a phosphorus atom, or wherein any two adjacent substituents R 8, R 10 and R 11 are bonded to form a saturated or unsaturated cyclic structure of 4 to 20 carbon atoms containing a cyclopentadienyl ring bond, said structure optionally containing one or a plurality of heteroatoms specified above;

R 12 can independently be hydrogen, linear or

I, a branched hydrocarbyl group having 1 to 20 carbon atoms, a saturated or unsaturated cycloaliphatic or aromatic group or a hydrocarbyl group having 1 to 20 carbon atoms containing one or more heteroatoms

Groups 14 to 16 of the Periodic Table of the Elements, preferably a silicon atom, an oxygen atom, a nitrogen atom, a sulfur atom and a phosphorus atom.

A variant of step (f) of the process of the invention is shown in Reaction Scheme 2.

Reaction scheme 2

xm x n x 1 g: Li [N (isoPr) ₂ / THF] - 78 ° C; h: VII / THF; i: NaBH ₄ or LiR ₁₂ 'or R ₁₂ MgX; 1: CuSO ₄ (toluene) + 110 ° C

The invention therefore further relates to a variant of the preparation of compounds of formula Ia, which can be also applied for the preparation of analogous products of the formula XIII wherein the substituents R, R _2, R _7, R _8, R _{9 /} R _10, R _n and R _i2 the above meanings and which includes the following steps:

(g) reacting the cyclic ketone of formula IX; wherein R _{9 /} R ₁₀ and R 11 are as defined above, with lithium amide to form a mixture of anions of formula Xa and anions of formula Xb;

mixtures of anions of formula (Xa) and anions of formula (Xb) with a brominated product of formula (VII), which is prepared as outlined above (i) by reducing the functional carbonyl group to an alcohol group using suitable reagents to form a compound of formula (Xa). to form a derivative of formula (XII) wherein R _{12 is} as defined above;

(1) dehydration of the derivative of formula XII obtained in step (i), to give the desired indenyl-cyclopentadienyl compound of the formula XIII, wherein are R _x, R _2, R ₇ 'R _8, R, R, R, _{X 1} and R ₂ above, defined meaning.

In step (g), the cyclic ketone of formula IX is reacted with a strong non-alkylating base in an ether solvent such as ethyl ether, tetrahydrofuran and dioxane, as the dissolution capacity of the latter may increase the reaction kinetics, but this does not mean that Usually, less polar solvents such as aromatic and / or aliphatic hydrocarbons are used at temperatures ranging from -80 ° C to +110 ° C, depending on the type of solvent and substrates used.

^1. · ·.

Typical strong bases suitable for this purpose are alkali metal and alkaline earth metal alcoholates such as lithium methoxide, sodium methoxide, sodium ethoxide, sodium isopropoxide, sodium tert-butoxide, magnesium ethoxide, and the like. Or related amides such as lithium amide, sodium amide, lithium diethylamide, lithium diisopropylamide, lithium bis (trimethylsilyl) amide, potassium dibutylamide, and the like.

In a preferred embodiment, the strong bases are selected from the group consisting of lithium methoxide, sodium ethoxide, potassium tert-butoxide, sodium amide and lithium diisopropylamide.

In an even more preferred embodiment, the strong base is lithium diisopropylamide.

Typical cyclic ketone compounds of formula (IX) that may be suitably used in step (g) of Reaction Scheme 2 are: cyclopent-1-en-3-one, 1-methylcyclopent-1-en-3-one, 1,2 5-trimethylcyclopent-1-en-3-one, indan-1-one, 3-methylindan-1-one, 4,7-dimethylindan-1-one, indan-2-one, etc.

In a preferred embodiment, the cyclic ketone compound of formula IX is selected from cyclopent-1-en-3-one, 1,2,5-trimethylcyclopent-1-en-3-one, indan-1-one, 3-methyl-indan- l-one; and in an even more preferred embodiment, the compound of Formula IX is indan-1-one.

Step (h) of the process of the invention consists in reacting mixtures of an anion of formula (Xa) and an anion of formula (Xb) with a brominated product of formula (VII) prepared according to Reaction Scheme 1, which reaction may be carried out in a hydrocarbon or ether solvent. as a rule, it is preferable to use the same solvent as in previous step (g) at temperatures ranging from -80 ° C to + 70 ° C.

In a preferred embodiment, the reaction is carried out in a mixture of THF and hexane at temperatures ranging from -70 ° C to +25 ° C.

Step (i) of the process of the invention consists in reducing the functional carbonyl group of a derivative of formula XI to an alcohol group to give a compound of formula XII. For this purpose, there is a wide variety of suitable reducing agents known to those skilled in the art, such as, for example, aluminum hydride, sodium borohydride, sodium hydride, methyl lithium, phenyl lithium, ethyl magnesium bromide, isopropyl magnesium bromide, and the like. successfully used in either a hydrocarbon or ether solvent or mixtures thereof at temperatures ranging from -40 ° C to + 70 ° C. In a preferred embodiment, sodium borohydride in tetrahydrofuran is used at temperatures ranging from -20 ° C to +25 ° C.

Step (1) of the process according to the invention consists in dehydrating the derivative of the formula XII obtained in step (i) to give the desired indenylcyclopentadienyl product of the formula XIII.

This dehydration may be carried out in the presence of dehydrating agents such as silica gel, strong acids such as hydrochloric acid, sulfuric acid, paratoluenesulfonic acid or anhydrous inorganic salts such as Cu (SO ₄ ), Mg (SO ₄ ), Na (SO ₄ ) ₂ , CaCl _2, etc.

The scope of choice of solvent for this reaction is very wide, because for example, for example, solvents, solvents, solvents, nonpolar aliphatic hydrocarbons, medium polar aromatic hydrocarbons, or polar ethers or chlorinated hydrocarbons can be used successfully;

the temperature at which the reaction will take place can also be chosen from a very wide temperature range, typically temperatures ranging from -20 ° C to +130 ° C, and the choice of temperature generally depends not only on the substrate but also on the type of solvent used. In a preferred embodiment, anhydrous Cu (SO ₄ ) in toluene at +110 ° C is used.

The processes of the invention do not necessarily require isolation of the individual reaction products at the end of the individual steps.

In addition to the advantage of readily available starting products, another advantage of the methods of the invention is the relatively simple chemical processes and the production of satisfactory overall yields.

The preparation of complexes of formula (I) may be carried out by any of the known methods described in the literature in connection with the production of bridged biscyclopentadienyl complexes.

The most commonly used method involves reacting a metal salt of M (preferably chloride) with an alkali metal salt and a dianion of a biscyclopentadienyl ligand of the desired structure.

Generally, the preparation of complexes of formula (I) comprises two steps, in which the ligand of formula (Ia) is reacted with an alkyllithium such as methyllithium or butyllithium in an inert solvent, preferably consisting of an aromatic hydrocarbon or ether, and in particular tetrahydrofuran or ethyl ether. .

The temperature is preferably maintained below room temperature during the reaction, avoiding secondary reactions. At the end of the reaction, the corresponding lithium salt of the cyclopentadienyl dianion is obtained.

In a second step, the cyclopentadienyl dianion salt is reacted with a salt, preferably a chloride, of a transition metal, again in an inert organic solvent and at a temperature that is preferably in the range of -30 ° C to +70 ° C.

At the end of the reaction, the complex of formula I thus obtained is separated and purified by methods of organometallic chemistry known.

As known to those skilled in the art, the above described operating steps are sensitive to the presence of air and moisture and should therefore be carried out under an inert atmosphere, preferably under nitrogen or argon.

A variety of general and specific methods, which are essentially based on the method outlined above, are described in the literature, for example, in D. J. Cardin, "Chemistry of Organo Zr and Hf Compounds, J. Wiley and Sons Ed., New York (1986); R. Haltermann "Chemical Review, Vol. 92 (1992) p. 965 to 994; R. O. Duthaler and A. Hafner "Chemical Review, Vol. 92 (1992) p. 807 to 832.

The metallocene compounds of the present invention may conveniently be used as catalyst components for the. olefin polymerization.

Accordingly, a further object of the invention relates to an olefin polymerization catalyst comprising a reaction product:

(A) the metallocene compounds of formula I obtained as described above, and (B) one or more compounds which are capable of activating the metallocene compound of formula I and which are, in particular, known in the art, organic derivatives of the M ¹ elements which are not is carbon and is selected from elements 1, 2, 12, 13 and 14 of the Periodic Table of the Elements.

According to the invention, the element M 'is preferably selected from boron, aluminum, zinc, magnesium, gallium and tin, preferably selected from boron and aluminum.

In a preferred embodiment of the invention, component (B) is an organic oxygenated derivative of aluminum, gallium or tin. This derivative can be defined as an organic compound of element M 'in which M' is attached to at least one oxygen atom and to at least one organic group formed by an alkyl group having 1 to 12 carbon atoms, preferably a methyl group.

According to this aspect of the invention, component (B) is preferably an aluminoxane. It is known that aluminoxanes are compounds that contain A1-O-A1 bonds, with the 0 / A1 ratio varying. These compounds may be obtained by reacting an alkyl aluminum or alkylaluminium halide with water or other compounds containing predetermined amounts of available water, such as, for the triethylaluminum reaction, for example aluminum sulfate hexahydrate, copper sulfate pentahydrate or iron sulfate pentahydrate, and the like.

The aluminoxanes which are preferably used to prepare the polymerization catalyst of the invention are oligomeric, polymeric, cyclic and / or linear compounds which are characterized by the presence of repeating units of the following general formula:

wherein R 13 is C 1 -C 12 alkyl, preferably methyl.

Each dialuminoxane molecule preferably contains 4 to 70 repeating units, all of which may not be identical, but may contain different R ₁₃ groups.

In the preparation of the polymerization catalyst according to the invention, the aluminoxanes are contacted with the complex of the formula I in such a ratio that the ratio of atoms between the aluminum and the transition metal M ranges from 10 to 10,000 and preferably from 100 to 5,000. the complex of formula (I) and the aluminoxane are brought into contact with each other, it is not of interest to the invention.

In addition to the aluminoxanes described above, the definition of component (B) according to the invention also includes galloxanes (for which the preceding formulas may be used except that they contain gallium instead of aluminum) and stannoxanes whose use as cocatalysts in olefin polymerization in the presence of metallocene complexes U.S. Patent Nos. 5,128,295 and 5,258,475.

According to a further preferred embodiment of the invention, the catalyst can be obtained by contacting component (A) formed by at least one complex of formula I with a component (B) consisting of organometallic compounds complexed with a general group R ¹ on at least one compound or mixture of element M which are capable of extracting the formula I to form at least one side and react ionically with.

a neutral compound thereof, a compound comprising a metal M metallocene cation and an organic non-coordinating anion metal M ', the negative charge of which is delocalized on a multi-center structure, on the other hand.

Components (B) suitable as ionization systems of the above type are preferably selected from bulky organic boron and aluminum compounds, such as those represented by the following general formulas:

[(R _C ) _X NH _4] . _X ] ⁺ [B (RD) 4] '; B (Rd) 3; [Ph 3 C] ⁺ [B (R d) ₄ ] ';

[(R _C ) ₃ PH] ⁺ [B (RD) 4] [Li] ⁺ [B (RD) ₄ ] '; [Li] ⁺ [Al (R _D ) ₄ ] ';

wherein the deponent "x" represents an integer from 0 to 3, each R _c group independently representing an alkyl or aryl radical having 1 to 12 carbon atoms and each R _d group independently representing an aryl radical which is partially or preferably completely fluorinated and having 6 to 6 carbon atoms 20 carbon atoms.

Said compounds are generally used in amounts which provide a ratio between M 'of component (B) and M of component (A) of 0.1 to 15, preferably 0.5 to 10, and more preferably 1 to 6.

Component (B) may consist of a single compound, typically an ionic compound, or a combination of this compound with an MAO or, preferably, a trialkyl aluminum having 1 to 16 carbon atoms in each alkyl moiety such as AlMe ₃ , AlEt ₃ , Al (isoBu) ₃ .

The ionic metallocene catalyst of the invention is generally prepared in an inert liquid medium, more preferably in a hydrocarbon. The choice of components (A) and (B) whose combination with one another will be advantageous and the particular preparation method will depend on the molecular structures and the desired result, taking into account the results detailed in the literature available to those skilled in the art. .

Examples of these methods are summarized in the following in qualitative terms, which, as it should be noted, do not limit the scope of the invention. Ionic metallocene catalysts can be prepared by:

(i) of a metallocene compound of formula I, wherein at least one of X, _X and X _2, and preferably both of these substituents is hydrogen or an alkyl radical, with an ionic compound whose cation is capable of reacting with one of R X _x and X ₂ to form a neutral compound and whose anion is a bulky noncoordinating anion and is capable of delocalizing a negative charge;

(ii) indicating the metallocene compound of formula

Even with an alkylating agent, preferably a trialkylaluminum which is used in a molar excess of 10: 1 to 500: 1, followed by reaction with a strong Lewis acid, such as tris (pentafluorophenyl) boron, in a more or less stoichiometric in an amount or in a slight excess relative to the metal M;

(iii) contacting a metallocene compound of formula I with a molar excess of 10: 1 to 1000: 1, preferably 30: 1 to 500: 1, a trialkyl aluminum or an alkyl aluminum halide or one of their mixtures, which can be represented by the formula AlR _m X ₃ . _m wherein R represents a linear or branched alkyl group having 1 to 12 carbon atoms, X represents a halogen atom, preferably a chlorine atom or a bromine atom, and "m represents a decimal number from 1 to 3; and subsequently adding at least one ionic compound of the type described above in an amount that provides a ratio of bromine or aluminum atoms to M atoms in the metallocene complex of from 0.1 to 20, preferably from 1 to 6.

Examples of ionizing ionic compounds or multicomponent reaction systems capable of producing an ionic catalyst system by reaction with a metallocene complex of the invention are described in the following patent publications, the contents of which are incorporated herein by reference:

European patent applications, published under the following numbers:

EP-A 277 003, EP-A 277 004. EP-A 522 581. EP-A 495 375, EP-A 520 732. EP-A 478 913, EP-A 468 651 EP-A 427 697, EP-A-421 659. EP-A 418 044; '

International patent applications published under numbers:

WO 92/00333; WO 92/05208; WO 91/09882; and U.S. Pat. Nos. 5,064,802, 2,827,446 and 5,066,739.

Also included within the scope of the invention are those catalysts which contain a mixture of two or more complexes of the general formula I. The catalysts according to the invention based on complex mixtures having different catalytic activities can be advantageously used in polymerization where a broad molecular distribution is desired. by weight of the polyolefins thus prepared.

According to one aspect of the invention, the components of the aforementioned complexes used for the production of olefin polymerization catalysts may be deposited on inert solids, preferably consisting of silicon and / or aluminum oxides such as silica, alumina or aluminosilicates.

Known techniques can be used to deposit the above catalysts, typically by contacting the support, optionally activated by heating to a temperature above +200 ° C, with one or both of the components (A) and (B) of the catalyst of the invention. components in a suitable inert liquid medium. For the purposes of the invention, it is not necessary for both components to be supported on the support, and it is therefore also possible for only the complex of the general formula I or the organic boron, aluminum, gallium or tin compound as defined above to be present on the support surface. In this case, the component that is not present on the surface of the support is then contacted with the component on the support at the time of activation of the catalyst for polymerization purposes.

The invention also encompasses complexes and catalyst systems that have been deposited on a solid by functionalizing these complexes or catalyst systems and forming a covalent bond between the solid and the above-defined metallocene complex of Formula I.

A suitable process for preparing the supported catalyst of the invention comprises prepolymerizing a relatively small fraction of monomer or monomer mixture in the presence of a catalyst, the prepolymer being in the form of solid microparticles which are subsequently introduced into the polymerization reactor itself to complete the polymerization process in the presence of additional olefin (s). This method provides better control of the morphology and dimensions of the polymeric particles obtained at the end of the polymerization.

Optionally, at least one additional additive or component may be added to the catalyst of the invention, as well as components (A) and (B), in order to satisfy the particular requirements and provide a suitable catalyst system for the particular conditions. Such catalyst systems also fall within the scope of the invention. Additives or ingredients that may be included in the compositions and / or formulations of the catalysts of the invention are inert solvents such as aliphatic and / or aromatic hydrocarbons, aliphatic and aromatic ethers, weakly coordinating additives (Lewis bases) selected from, for example, non-polymerizable olefins, ethers, tertiary amines. and alcohols, halogenating agents such as silicon halides, halogenated hydrocarbons, preferably chlorinated, etc. as well as all other possible components which are generally used in the preparation of traditional homogeneous metallocene-type catalysts intended for the (co) polymerization of olefins.

The components (A) and (B) form the catalyst according to the invention by contacting one another, preferably at temperatures ranging from +20 ° C to +60 ° C and lasting for 10 s to 1 h, more preferably 30 sec. To 15 min.

The catalysts according to the invention can be used with excellent results in virtually all known (co) polymerization processes for the production of olefins, which are carried out either continuously or batchwise, in one or more steps, at low (0.1 MPa to 1.0 MPa). MPa), medium (1.0 MPa to 10 MPa) or high (10 MPa to 150 MPa) pressure and at temperatures ranging from + 10 ° C to +240 ° C, optionally in the presence of an inert diluent. Hydrogen can conveniently be used as the molecular weight regulator.

These methods may be carried out in solution or suspension in a liquid diluent, typically consisting of an aliphatic or cycloaliphatic saturated hydrocarbon having from 3 to 20 carbon atoms, or a mixture of two or more of these hydrocarbons, but the liquid diluent may also be a monomer such as in a known process of copolymerizing ethylene and propylene in liquid propylene. The amount of catalyst to be introduced into the polymerization mixture is preferably chosen such that the concentration of metal M varies from

10 to ⁴ mol / l to 10 to ⁸ mol / l.

Alternatively, the polymerization can be carried out in the gas phase, for example in a fluidized bed reactor, typically at a pressure of 0.5 to 5 MPa and at temperatures ranging from +50 ° C to +150 ° C.

According to one particular aspect of the invention, the catalyst for (co) polymerization of ethylene with other olefins is prepared separately (in advance) by contacting component (A) with component (B) and subsequently introducing it into the polymerization medium.

First, the catalyst is placed in the polymerization reactor and then the reaction mixture containing the olefin or mixture of olefins to be polymerized, or the catalyst is placed in a reactor that already contains the reaction mixture, or the reaction mixture is introduced into the reactor simultaneously with the catalyst.

According to another aspect of the invention, the catalyst is formed in situ, for example by introducing component (A) and component (B) separately into a polymerization reactor containing pre-selected olefin monomers.

The catalysts according to the invention can be used with excellent results in the polymerization of ethylene to give linear polyethylene and in the copolymerization of ethylene with propylene or higher olefins having preferably 4 to 12 carbon atoms and resulting in copolymers having different properties depending on the particular used. polymerization conditions and the amount and structure of the comonomer used.

For example, linear polyethylenes having a density of 0.880 to 0.940 and having a molecular weight in the range of 10,000 to

The olefins preferably used as ethylene comonomers in the manufacture of low-density or medium-density linear polyethylene (known under the abbreviations ULDPE, VLDPE and LLDPE depending on density) are 1-butene, 1-hexene and 1-octene. ¹ ,

The catalyst of the present invention can also be commonly used in and propylene which is extremely copolymerization of ethylene elastomeric copolymers, are decomposition peroxides, and which are non-conjugated and which have 4 carbons, and which copolymerization which, or generally providing saturated, can be vulcanized by resistant aging and ethylene, propylene, and a diene of up to 20 atoms will yield vulcanizable EPDM type gums.

In the processes cited in the immediately preceding paragraph, it has been found that the catalysts of the invention make it possible to produce polymers having a very high comonomer content and an average molecular weight under polymerization conditions.

In the case of the preparation of EPDM, the dienes which are suitable for this purpose are preferably selected from:

• linear chain dienes such as

1,4-hexadiene and 1,6-octadiene;

Branched dienes such as 5-methyl-1,4-hexadiene; 3,7-dimethyl-l, 6-octadiene; and 3,7-dimethyl-1,7-octadiene;

Single ring dienes such as 1,4-cyclohexadiene; 1,5-cyclooctadiene; 1,5-cyclododecadiene; and dienes having bridged fused rings such as dicyclopentadiene; bicyclo [2.2.1] hepta-2,5-diene; alkylene, alkylidene, cycloalkenyl and cycloalkylidene norbornenes such as 5-methylene-2 norbornene, 5-ethylidene-2-norbornene (ENB) and 5-propenyl-2-norbornene.

With regard to the unconjugated dienes which are generally used in the preparation of these copolymers, for example, dienes containing at least one ring double bond, and more preferably 5-ethylidene-2-norbornene (ENB) as well as 1,4-hexadiene are preferred. and 1,6-octadiene.

In the case of EPDM terpolymers, it is common that the amount of diene monomer does not exceed 15% by weight, and preferably ranges from 2% by weight. % to 10 wt. The propylene content ranges from 20% by weight. % to 55 wt.

The catalysts according to the invention can also be used in the homopolymerization and copolymerization of olefins, which are carried out according to known techniques and which in excellent yields provide atactic, isotactic or syndiotactic polymers, depending on the structure and geometry of the metallocene complex of the formula I.

Olefins suitable for this purpose contain from 3 to 20 carbon atoms, optionally also containing halogen atoms and / or other heteroatoms or aromatic nuclei, for example propylene, 1-butene, 1-hexene, 1-octene, 4-methyl-1-pentene, -decene and styrene.

The following examples are illustrative only and are not intended to limit the scope of the invention, which is clearly defined by the appended claims.

Analytical methods used

Analytical techniques and determining methods that have been used in the Examples below will now be described.

The characterization by means of NMR spectroscopy mentioned in the following examples was a nuclear magnetic resonance spectrometer Bruker MSL-300, and as the solvent, unless otherwise specified, is used for each sample CDC1 _third

The molecular weight of olefin polymers was determined using gel permeation chromatography (GPC). Samples were analyzed in 1,2,4-trichlorobenzene (stabilized with Santonox) at +135 ° C in a WATERS 150-CV chromatograph using a Waters differential refractometer as a detector. Chromatographic separation was achieved with a set of μ-Styragel HT columns (Waters), three of which had a pore size of 10 ² nm, 10 ³ nm and 10 ⁴ nm, respectively, and two had a pore size of 10 ⁵ nm, with the eluent flow rate set to 1. ml / min, Data was collected and processed. using Maxima 820 software version 3.30 (Millipore); calculation of number (M _n ) and weight (M _w ) average molecular weight was done by universal calibration by selecting polystyrene standards with molecular weights of 6 500 000 to 2000 for calibration.

The determination of the propylene and optional diene-derived units in the polymers was carried out (by the Applicant method) by IR on the same polymers in the form of films having a thickness of 0.2 mm, using a FTIR Perkin-Elmer, model 1760 spectrophotometer. for the propylene measured at wavelengths 4390 cm ^-1 and the ENB at 1688 cm ^-1, and in relation to the peak at 4255 cm ^-1, the amount was found using a standard calibration curve.

The melt flow index (MFI) of the polymers was determined using ASTM D-1238 D.

The Mooney viscosity (1 + 4) was determined at +100 ° C using a Monsanto 1500 viscometer with the ASTM D 1646/68 method.

DETAILED DESCRIPTION OF THE INVENTION

Example 1

Synthesis of 1-methyl-4-methylene (1-indenyl) indene

The following products are reacted:

170 ml benzene,

Crotonic acid 22.7 g (264 mmol) a

106 g (795.2 mmol) of aluminum chloride.

A1C1 ₃

J

A solution of crotonic acid in 100 mL of benzene was added dropwise to a suspension of AlCl 3 in 70 mL of benzene.

The resulting mixture was stirred at + 80 ° C for 5 h. Pour on ice and extract with ethyl ether. After washing with saturated aqueous NaHCO ₃ solution and water until neutrality and drying over Na ₂ SO ₄ , the solvent was evaporated. The product is purified by distillation (t r = + 125 ° C). 32.0 g of the expected product are obtained (83% yield).

The 32.0 g (219.2 mmol) of 3-methyl-1-indanone obtained in the previous step is reacted with:

5.6 g (147 mmol) of sodium borohydride,

128 ml of tetrahydrofuran and ml of methanol.

To a solution of 3-methyl-1-indanone in tetrahydrofuran and methanol was added portionwise at 0 ° C NaBH ₄ . After 2 h, the mixture was poured onto ice and extracted with ethyl ether. After washing the organic extracts to neutrality with saturated NaCl solution and drying over Na ₂ SO ₄ , the mixture obtained is filtered and the solvent is evaporated. 30.8 g of product are obtained (95% yield).

14.8 g (0.1 mol) of 3-methyl-1-indanol obtained in the previous step are reacted with:

ml (0,2Mol) 2,5M LiBu in hexane,

26.7 ml (0.22 mol) of diethyl carbonate a

500 ml hexane.

Approximately 1 h, n-butyllithium is added to a suspension of 3-methyl-1-indanol in hexane under an inert atmosphere at + 20 ° C via a separatory funnel. After the addition was complete, the reaction mixture was warmed to + 60 ° C and kept at this temperature for 2 h, then cooled to -70 ° C and diethyl carbonate was added. The temperature is allowed to rise slowly to + 25 ° C and after a further 8 h the reaction mixture is poured into water and extracted with ethyl ether. The separated organic phase is washed with water until neutrality, dried over sodium sulfate and the solvent is evaporated off under reduced pressure. Purification by silica gel column chromatography (eluent: hexane / ethyl acetate 9: 1) gave 5.6 g of 3-methyl-7-carboethoxy-lindanol.

5.6 g (25.45 mmol) of 3-methyl-7-carboethoxy-1-indanol were reacted with:

ml of toluene and

0.1 g (0.58 mmol) of p-toluenesulfonic acid (PTSA).

Add p-toluenesulfonic acid to the solution

3-methyl-7-carboethoxy-1-indanol in toluene. The resulting mixture was heated to +100 ° C and water was removed by azeotropic distillation. After 2 h, saturated aqueous NaHCO ₃ solution is added, the organic phase is separated, washed with water until neutrality and dried over NaSO ₄ . Finally, the solvent is removed under reduced pressure and after purification by silica gel column chromatography (eluent:

hexane / ethyl acetate 95: 5), 5.0 g of 3-methyl-7-carboethoxy-lindene is obtained.

5.0 g (24.7 mmol) of 3-methyl-7-carboethoxy-1-indene was reacted with:

0.6 g (15.8 mmol) LiAlH ₄ a

100 ml of ethyl ether.

· OH

COOEt

A solution of 3-methyl-7-carboethoxy-1-indene in 40 mL of ethyl ether at -30 ° C was added to a suspension of LiAlH ₄ in 60 mL of ethyl ether. The temperature is gradually allowed to rise to + 25 ° C, after 30 min water is slowly added and the resulting mixture is acidified by the addition of 2M HCl. The reaction mixture is extracted with ethyl ether, rinsed repeatedly with water until neutrality, and dried over NaSO ₄ . The solvent was finally removed in vacuo to give 3.76 g of 7 (3-methylindenyl) methanol.

3.76 g (23.5 mmol) of 7- (3-methylindenyl) methanol are reacted with:

2.1 g (7.86 mmol) of PBr ₃ and ml of methylene chloride.

.OH .Br

bromide the phosphorous is slowly added by means of a separating funnel adds to solution of 7- (3-methylindenyl) methanol in CH ₂ C1 ₂ cooled at -20 ° C. The temperature is allowed to rise to

+ 25 ° C and after 30 min a saturated aqueous solution is slowly added

NaHCO ₃ . The reaction mixture is extracted several times with ethyl ether, the organic extracts are washed with water until neutrality and dried over NaSO ₄ . After removal of the solvent under reduced pressure, 4.9 g of 4-bromomethyl-1-methyl-indene is obtained.

The g (31.4 mmol) of the 4-bromomethyl-1-methylindene obtained in the previous step is reacted with:

ml (77.5 mmol) of 2.5 M LiBu ₂ in hexane,

200 ml THF and

7.3 ml (62.3 mmol) of indene.

ch ₃

Butyllithium is added dropwise to a solution of indene in 100 mL of THF. The resulting mixture was stirred at room temperature for 2 h and then cooled to -70 ° C. Bromine dissolved in THF is then added. After 1 h at this temperature, the resulting mixture was allowed to warm to room temperature and poured into water, then extracted with ethyl ether, the extracts were washed until neutrality and dried over sodium sulfate. The residue obtained by evaporation of the solvent was purified by column chromatography on silica gel using petroleum ether as eluent. 4.3 g of 1-methyl-4-methylene (1-indenyl) indene (53% yield) are thus obtained.

Example 2

Synthesis of 4-methylene (1-indenyl) indene

The following products are reacted:

16.0 g (119.4 mmol) of 1-indanol,

100 mL (250 mmol) of 2.5 M LiBu in hexane,

31.5 (259.6 mmol) of diethyl carbonate a

500 ml hexane.

LiBu o

N-Butyllithium is added dropwise to a suspension of 1-indanol in hexane at -5 ° C. The resulting mixture was stirred at + 60 ° C for 2 h and diethyl carbonate was added at -70 ° C. The temperature of the resulting mixture was allowed to rise to room temperature. After 8 h, it was poured into water and extracted with ethyl ether. After washing the organic extracts to neutrality and drying over Na ₂ SO ₄ , the solvent is evaporated in vacuo. The product was purified by chromatography on silica gel eluting with hexane / ethyl acetate (95: 5). 6 g of product are obtained (24.5% yield).

g (24.3 mmol) of the hydroxy ester obtained in the previous step is reacted with:

200 mg (1.05 mmol) of p-toluenesulfonic acid and ml of toluene.

The toluene solution of hydroxyester and PTSA were stirred at + 90 ° C for 3 h. The resulting mixture was washed to neutrality with saturated aqueous NaHCO ₃ and water. After drying the organic phase over Na ₂ SO ₄ and filtration, the solvent is evaporated. The residue was purified by column chromatography on silica gel eluting with hexane: ethyl acetate (95: 5). In this way, 4.0 g of ester was obtained (87.7% yield).

8.8 g (46.8 mmol) of the ester obtained in the previous step are reacted with:

2.1 g (55.3 mmol) of aluminum hydride a

120 ml of ethyl ether.

. The ester dissolved in 20 mL of ethyl ether is added to a suspension of LiAlH ₄ in ethyl ether at -20 ° C. After 6 h, water is slowly added, the resulting mixture is acidified by addition of HCl (2N) and extracted with ethyl ether. After washing the organic extracts to neutrality and drying over Na ₂ SO ₄ , the mixture obtained is filtered and the solvent is evaporated. 6.6 g of alcohol are obtained (96% yield).

The 6.6 g (45.2 mmol) of the alcohol obtained in the previous step is reacted with:

1.5 ml (15.82 mmol) of phosphorus tribromide and ml of methylene chloride.

PBr ₃

---->

Phosphorus tribromide at

-20 ° C was added dropwise to a solution of the alcohol in methylene chloride. After 1 h, a saturated aqueous NaHCO ₃ solution was added dropwise and the mixture was extracted several times with ethyl ether. After washing the organic extracts to neutrality and drying over Na ₂ SO ₄ , the mixture obtained is filtered and the solvent is evaporated. 5.0 g of 4-bromomethylindene are obtained (53% yield).

4.44 ml (33.6 mmol) of Indene are reacted with:

ml (33.6 mmol) of a 2.5 M solution of LiBu in hexane, g (24 mmol) of 4-bromomethylindene, ml of tetrahydrofuran and ml of hexane.

To a solution of indene in THF in hexane is added n-butyllithium at + 5 ° C. After 1 h the resulting mixture was cooled to -70 ° C and benzyl bromide dissolved in 20 mL THF was added. The temperature of the resulting mixture was allowed to rise to room temperature. After 8 h, the mixture was poured into water and extracted with ethyl ether. After washing the ether extracts to neutrality with water and drying over Na ₂ SO ₄ , the mixture obtained is filtered and the solvent is evaporated.

Purification by silica gel column chromatography (eluent: hexane) gave 2.3 g of 4-methylene- (1-indenyl) indene (39.3% yield).

Example 3

Synthesis of 7-methyl-4-methylene (4,7-dimethyl-1-indenyl) indene

The following reaction scheme is used for the synthesis:

ABOUT

The following products are reacted:

108.0 g (583.7 mmol) of o-methylbenzyl bromide,

150 ml (988 mmol) of dimethyl malonate,

21.4 g (930 mmol) of sodium,

350 ml of ethyl alcohol, g (445 mmol) of KOH, ml of thionyl chloride and g (285.7 mmol) of aluminum chloride.

Sodium metal is added portionwise to ethanol. Diethyl malonate is slowly added dropwise to a solution of sodium ethylate in ethanol at + 50 ° C and then omethylbenzyl bromide is added rapidly. The mixture was kept at reflux temperature for 2 hours with stirring. After evaporating most of the ethanol, the resulting mixture was poured into water and extracted with ethyl ether. After drying over Na ₂ SO ₄ , the solvent is evaporated under reduced pressure. The product is purified by distillation (T = + 125 ° C; P = 0.133 kPa). 50 g of monosubstituted diethyl malonate are obtained.

g Monosubstituted diethyl malonate dissolved in 75 ml of ethanol is added to a solution of KOH in 75 ml of water. The resulting mixture was stirred at + 80 ° C for 4 h. After removing the ethanol by evaporation under reduced pressure, the resulting mixture was acidified by adding HCl (1: 1) and extracted with ethyl acetate. After washing the organic extracts to neutrality and drying over Na ₂ SO ₄ , the solvent is evaporated under vacuum. 37.4 g of monosubstituted malonic acid are thus obtained.

The dibasic acid thus obtained is decarboxylated for 1 h at + 160 ° C to give 31.6 g of monobasic acid.

SOCl ₂ was added dropwise to the acid. The resulting mixture was stirred. After removal of excess thionyl 41 chloride, the acyl chloride is isolated by vacuum distillation. In this way it is obtained

31.0 g of acyl chloride.

Acyl chloride dissolved in 50 ml of methylene chloride is added to a suspension of AlCl ₃ in 400 ml of methylene chloride at + 10 ° C. The resulting mixture was stirred at room temperature for 1 h. Pour on ice and extract with ethyl ether. After washing the organic extracts to neutrality and drying over Na ₂ SO ₄ , the solvent is evaporated under vacuum. 22.0 g of product are obtained (26% overall yield).

22.0 g (150.7 mmol) of 4-methyl-1-indanone are reacted with:

3.9 g (102.6 mmol) of sodium borohydride, ml of tetrahydrofuran and ml of methanol.

To a solution of 4-methyl-1-indanone in THF / CH ₃ OH was added portionwise at 0 ° C NaBH ₄ . After 3 h, the mixture was poured into water and extracted with ether. After washing the organic extracts to neutrality and drying over Na ₂ SO ₄ , the solvent is evaporated under vacuum.

This way

4-methyl-1-indanol (99% yield).

22.0 g of 4-methyl-1-indanol (148.6 mmol) are reacted with:

123 ml (307 mmol) of a 2.5 M solution of n-butyllithium in hexane,

750 ml hexane a

39.1 ml (322 mmol) of diethyl carbonate.

n-Butyllithium is added to a solution of 4-methyl-1-indanol in hexane at 0 ° C. The resulting mixture was stirred at + 60 ° C for 2 h. diethyl carbonate is added dropwise at -70 ° C. The temperature of the resulting mixture was allowed to rise to room temperature. After 8 h, the mixture was poured into water and extracted with ethyl ether. After washing the organic extracts to neutrality and drying over Na ₂ SO ₄ , the solvent is evaporated. After purification by silica gel column chromatography (eluent: hexane / ethyl acetate = 9: 1),

6.9 g of product (21.2% yield).

12.5 g (56.8 mmol) of the hydroxy ester are reacted with: 400 mg (2.1 mmol) of p-toluenesulfonic acid (PTSA) and 100 ml of toluene.

PTSA is added to a toluene solution of hydroxyester. The resulting mixture was stirred at boiling point, the azeotrope and toluene removed by distillation. After 2 h, the resulting mixture was flushed to neutrality with saturated NaHCO ₃ solution, dried over Na ₂ SO ₄ and the solvent was evaporated. 10.0 g of product are obtained (87% yield).

1.1 g (28.9 mmol) of aluminum hydride a

200 ml of ethyl ether.

The ester dissolved in 60 ml of ethyl ether is added at -30 ° C via a separatory funnel to a suspension of LiAlH ₄ in ethyl ether. After 30 min at 0 ° C, water is slowly added followed by HCl (2N), followed by extraction with ethyl ether. After washing the organic extracts to neutrality and drying over Na ₂ SO ₄ , the solvent is evaporated under reduced pressure. 7.8 g of alcohol are obtained (99% yield).

8.8 g (55 mmol) of the alcohol are reacted with:

1.77 ml (18.15 mmol) of phosphorus tribromide a

110 ml of methylene chloride.

PBr _{3 is} added dropwise to the solution of alcohol in CH ₂ Cl ₂ at -20 ° C. After 30 min, saturated aqueous NaHCO ₃ solution is slowly added until the pH is basic. The resulting mixture is extracted with ethyl ether and rinsed until neutral with water. After drying over Na ₂ SO ₄ solvent, 7.8 g of product is obtained (64% yield).

and evaporation

Preparation of 4,7-dimethylindenyllithium

h ₂ Sat _{4 y}

The following products are reacted:

14.5 g (137 mmol) of p-xylene, g AlCl ₃ , ml (104.7 mmol) of 3-chloropropionyl chloride, ml of methylene chloride and ml of concentrated H ₂ SO ₄ .

I. ‘«

A solution of 3-chloropropionyl chloride in xylene is allowed to drip into a suspension of AlCl ₃ in methylene chloride for about 1 hour while maintaining the temperature at 0 ° C and under an inert atmosphere. After the addition is complete, the temperature of the mixture obtained is allowed to rise to + 10 ° C and is maintained at a temperature range of + 10 ° C to + 20 ° C for approximately 2 hours. The mixture was poured onto ice and extracted with methylene chloride.

The organic extracts are washed with water until neutrality and then dried over sodium sulfate.

The residue obtained by evaporation of the solvent is added to H ₂ SO ₄ at a rate of addition at which the temperature is maintained at + 20 ° C to + 30 ° C. After the addition was complete, the resulting mixture was heated to + 80 ° C and maintained at this temperature for 2 h. The resulting mixture was then poured onto ice and extracted with ethyl ether. The ether solution was washed to neutrality with saturated sodium bicarbonate solution followed by water and dried over sodium sulfate. The solid obtained by evaporation of ether is rinsed with petroleum ether and dried.

20 g of 4,7-dimethyl-1-indanone are thus obtained (91% yield over two passages).

2.9 g (18.1 mmol) of 4,7-dimethyl-1-indanone are reacted with:

0.35 g (9.2 mmol) of LiAlH ₄ , ml of ethyl ether, ml of THF and

0.2 g (1.05 mmol) of p-toluenesulfonic acid (PTSA).

In an inert atmosphere, indanone is slowly added to a suspension of LiAlH ₄ maintained at -30 ° C. After 30 min, the reaction is complete. Ice and 2N HCl are carefully added, the mixture is extracted with ethyl ether and rinsed to neutrality, dried over sodium sulfate and the solvent is evaporated. The obtained indanol was dissolved in 10 ml of THF, p-toluenesulfonic acid was added and the mixture was refluxed for 1 h.

Solid NaHCO ₃ and Na ₂ SO ₄ are then added. The mixture was filtered and, after evaporation of the solvent, 2.4 g of 4,7-dimethylindene were obtained (91% yield). ¹

7.4 g (51.4 mmol) of 4,7-dimethylindene are reacted with; _b .

32.3 ml (51.6 mmol) of a 1.6 M solution of LiBu in hexane,

7.8 g (35.1 mmol) of benzyl bromide,

297 ml tetrahydrofuran and

148 ml hexane.

LiBu. is added. to a solution of 4,7-dimethylindene in THF and hexane. After 2 h, bromine dissolved in 20 mL THF and 10 mL hexane was added at -70 ° C. The mixture was allowed to warm to room temperature, water was added after 8 h, and the mixture was extracted with ethyl ether. After washing the organic extracts to neutrality and drying over Na ₂ SO ₄ , the solvent is evaporated. Purification by column chromatography on silica gel, eluting with hexane / ethyl acetate 98: 2, afforded 3.1 g of the product (31% yield).

Example 4

Synthesis of 4-methylene (2-indenyl) indene

The following products are reacted:

11.2M1 (79.8 mmol) of diisopropylamine, ml (72.5 mmol) of a 2.5M solution of LiBu in hexane,

9.5 g (72 mmol) of 1-indanone a

6.0 g (28.8 mmol) of 4-bromomethylindene.

LiBu was added dropwise at -20 ° C to a solution of diisopropylamine in 70 mL of THF. After 40 min, a 2M solution was added at -70 ° C

Of 1-indanone in THF. After 90 min, a 2M solution was added

Of 4-bromomethylindene (prepared according to Example 2) in THF. The temperature of the resulting mixture was allowed to rise to room temperature. After 30 min, the mixture was poured into water and extracted with ethyl ether. After rinsing the organic extracts to neutrality with saturated aqueous NH ₄ Cl solution and water, it is dried over Na ₂ SO ₄ and the solvent is evaporated. 14 g of crude product are obtained

4-methylene (2-indan-l-one) indene are obtained.

NaBH4

---- ►

OH

13.8 g of crude 4-methylene (2-indan-1-one) indene are reacted with:

2.6 g (68.42 mmol) of sodium borohydride,

120 ml of tetrahydrofuran and ml of hexane. .

To a solution of 4-methylene (2-indan-1-one) indene in THF and hexane was added NaBH ₄ at -20 ° C. The temperature of the resulting mixture was allowed to rise to room temperature. After 2 h, water was added and the resulting mixture was extracted with ethyl ether. After rinsing the organic extracts to neutrality with a saturated aqueous solution of NH ₄ Cl. After drying over Na ₂ SO ₄ , the solvent is evaporated. 13.0 g of crude 4-methylene (2-indan-1-ol) indene are obtained.

CuSO ₄

13.0 g of crude 4-methylene (2-indan-1-ol) indene is reacted with:

15,0 g of anhydrous copper sulphate and

100 ml toluene.

Alcohol is added to a suspension of CuSO ₄ in toluene. After 90 min at + 110 ° C the mixture was poured into water and extracted with ethyl ether. After washing the organic extracts to neutrality with water and drying over Na ₂ SO ₄ , the solvent is evaporated. In this way, after purification by column chromatography on silica gel (eluent:

hexane / ethyl acetate = 99: 1) to give 1.8 g of 4-methylene (2-indenyl) indene.

Example 5

Synthesis of 1-methyl-4-methylene (1R) ^5- indenyl) -η ⁵ -indenylzirconium dichloride

The following products are reacted:

2.4 g (9.3 mmol) of 1-methyl-4-methylene (1-indenyl) indene, cm ³ (24 mmol) of a 1.6 M solution of LiBu in hexane, cm ^{3 of} ethyl ether and

1.7 g (5.6 mmol) of ZrCl _fourth

LiBu was added to an ethereal solution of 1-methyl-4-methylene (1-indenyl) -indene via a separatory funnel; approximately after adding

half quantity the starts from lithium salt solution is a dark White. The mixture obtained the allowed

Form a precipitate corresponding to yellow while the precipitate is stirred overnight. DCI Control (methyl iodide-treated sample) shows the presence of ligand, monobasic salt and dibasic salt in approximately equimolar amounts. Another 10 cm ^{3 of} LiBu are then added. GC Mass analysis reveals the presence of a dibasic salt with a trace amount of the monobasic salt and the absence of a ligand. The resulting mixture was stirred for 1 night.

The lithium salt is decanted, rinsed several times with hexane and finally dried under vacuum. The solid is suspended in approximately 80 cm ^{3 of} toluene, cooled to -70 ° C, and then zirconium chloride is added. The temperature was allowed to rise spontaneously to room temperature and the mixture was allowed to stir for an additional 30 min. The suspension (dark red) was filtered and rinsed with toluene (3 x 10 mL) followed by methylene chloride (3 x 10 mL).

The filtrate is concentrated, and a pitch product is observed which is isolated by filtration. The liquid solution was dried and ethyl ether was added to the residue. The complex is separated from the resulting solution as a yellow solid.

^X H NMR (mg / 1, based on TMS)

7.50-7.15 (m, 4H); 7.13-6.90 (m, 3H); 6.73 (d, 1H, J = 3.1Hz);

6.63 (d, 2H, J = 2.6Hz); 6.54 (d, 1H, J = 3.0Hz); 4.53 (d, 1H, J = 14.0Hz); 4.32 (d, 1H, J = 14.0Hz); 2.44 (s, 3H).

Examples 6 to 9

Copolymerization of ethylene and propylene

Examples 6 to 9 refer to a series of copolymerization tests for the preparation of elastomeric polymers of the EPR type based on ethylene and propylene, which are carried out using a catalyst system comprising a catalyst metallocene complex 1-methyl -4-methylene (1 - η ⁵ - indenyl) -η ⁵ - indenylzirkóniumdichloridu , obtained in Example 5 above, and methyl-alumoxane (MAO) as a cocatalyst. The specific polymerization conditions for each example and the results obtained are summarized in Table 1 below, which gives the following order: reference number of the example, amount of zirconium used, ratio of atoms between aluminum in MAO and zirconium, total polymerization pressure, catalyst system efficiency based on zirconium, the relative weight amount of C ₃ monomer units in the polymer, the weight average molecular weight M _w and the ratio of weight and number average molecular weight M _w / M _{n The} polymerization is carried out in a 0.51 liter pressure reactor equipped with a magnetic anchor stirrer and an outer jacket connected to a thermal a heat exchanger that ensures temperature control in the reactor. The reactor is first flushed for at least 2 hours while maintaining a vacuum (0.1 Pa) at + 80 ° C.

120 g of liquid propylene of suitable polymerization quality are introduced into the reactor at + 23 ° C. The reactor is then heated to a polymerization temperature of + 40 ° C and ethylene gas of suitable polymerization quality is introduced into the reactor through a tube until the desired equilibrium pressure (2.0 MPa to 2.7 MPa) is reached. Under these conditions, the molar concentration of ethylene in the liquid phase is from 11 mol%. up to 23 mol%, depending on the total system pressure, as can be easily calculated using suitable liquid and vapor tables.

In a suitable tube under nitrogen is introduced as MAO 1.5 M solution (as Al) in toluene (commercial product Eurecene 5100 10T of Witco) and the desired amount of the above described metallocene complex, as a toluene solution generally having a concentration of 3 x 10 ^-4 mol and 1 x 10 ^-3 mol. The catalyst solution thus prepared is kept at room temperature for several minutes and then transferred under an inert gas stream to a metal vessel from which it is introduced into the reactor by means of nitrogen overpressure.

Polymerization necessary to be careful by continuous introduction of the reacted part of the interrupted and remaining ethyl alcohol

1000 Pa. Thus the reaction is carried out at +40 ° C while maintaining the total constant pressure of ethylene. polymerization of monomers.

at least 8 ethylene obtained, which. it already compensates for the introduction of ethylene by removal

After 15 min, stop

The polymer is dried by rapid isolation, the solid is calculated as at +60, the material is rinsed, and the polymer efficiency is measured at ° C.

The propylene content is determined on a sample of dry homogenised solid kilogram of zirconium metal catalyst per hour (kg _after i./g _Zr · h).

units per substance using known techniques based on IR spectroscopy, per gram, together with weight (M _w ) and number (M _n ) average molecular weight. The results are summarized in Table 1.

Examples 10 to 12

Examples 10 to 12 relate to a series of copolymerization tests for the preparation of ethylene-propylene-based EPR-type elastomeric polymers which are carried out using a catalyst system comprising the metallocene complex obtained in Example 5 above, alkyl aluminum and a suitable boron compound as a cocatalyst.

In Examples 10 to 12, the procedure described in Examples 6 to 9 is followed with the following variations.

At + 23 ° C, 120 g of liquid propylene of suitable polymerization quality and the exact amount of Al (isoBu) _{3 are} introduced into the reactor so as to obtain an aluminum concentration corresponding to 5 x 10 ^-3 mol / l. The reactor is then heated to a polymerization temperature of +40 ° C and gaseous ethylene of suitable polymerization quality is fed through the tube until the desired equilibrium pressure (2.0 MPa to 2.7 MPa) is reached. Under these conditions, the molar concentration of ethylene in the liquid phase is from 12 mol%. up to 23 mol%, depending on the total system pressure, as can be easily calculated using suitable liquid and vapor tables. ¹

In a suitable tube under nitrogen is introduced Al (iso-Bu) ₃ as an 0.4 M solution in toluene and the desired quantity of metallocene complex, prepared as in Example 5, as a toluene solution generally having a concentration of 3 x 10 ^-4 mol to lx 10 ^"3 M . The catalyst solution thus prepared is kept under stirring at + 23 ° C for 15 min, immediately thereafter a concentration of toluene solution having generally

5 x 10 ^-4 mol to lx 10 ^"3 mol of [CPh _3] [B (C ₆ F _{5) 4],} and after a few minutes, is transferred under a stream of inert gas to a metal container from which it is introduced by means of an overpressure of nitrogen in the reactor.

The results are summarized in Table 2.

Table 1

C ₂ / C ₃ copolymerization tests with catalytic system formed

1-methyl -4-methylene (1 - η ⁵ - indenyl) -η ⁵ - indenylzirkóniumdichloridom and MAO

Example Zr Al / Zr ^ total Efficiency. C3 (polymer) M _w M _w / M _n number (mol10 ⁶ ) (Mol / mol) (MPa) (Kgpoi./gzr-h) (% by weight) (x 10 ³ ) 6 1.75 1975 2.0 218 62 89 2.8 7 1.30 2385 2.2 806 55 134 2.9 8 0.65 3950 2.5 • 3275 44 208 2.4 9 0.38 5980 2.7 6070 39 317 2.2

Table 2

C ₂ / C ₃ copolymerization tests carried out using a catalytic system formed

1-methyl-4-methylene (1-rf-indenyl) -η ⁵ indenylzirconium dichloride, Al (isoBu) ₃ and CPh ₃ [Β (Ο ₆ Γ ₅ ) ₄ ]

Example Zr Al / Zr B / Zr P total effective ^ 3 (polymer) M _w M _w / M _n number (mol · 10 ⁶ ) (Mol / mol) (Mol / mol) (MPa) (kg _after i./g _zr -h) (% by weight) (x 10 ³ ) 10 1.1 350 1.1 2.2 567 48 162 3.1 11 0.9 350 1.1 2.5 1758 41 237 2.6 12 0.6 350 1.1 2.7 2749 35 330 2.4

Claims (14)

PATENT CLAIMS 1. Metallocene compounds of formula I: I, where: R 1 and R ₂ may be in any free positions of the indene group; R, R 2, R 3 / R _4, R, R, R 7 and R _a are independently hydrogen, halogen, preferably F, Cl or Br, a linear or branched, saturated or unsaturated, cycloaliphatic or aromatic hydrocarbyl C 1 hydrocarbyl with up to 20 carbon atoms; or 1 to 20 carbon atoms substituted with one or more halogen atoms, or a hydrocarbyl group having 1 to 20 carbon atoms containing one or more heteroatoms selected from Groups 14 to 16 of the Periodic Table of the Elements, preferably selected from silicon, oxygen, nitrogen, sulfur and phosphorus; in addition, any two of R _3, R _4, R _s and R ₆ or both of the pairs of substituents R _3, R _4, R ₅ and R _6, adjacent to each other, are joined to form a saturated or unsaturated cyclic structure, having from 4 to 20 carbon atoms containing a cyclopentadienyl ring bond, said structure optionally having one or more heteroatoms specified above; M is a metal atom selected from the group consisting of titanium, zirconium or hafnium; X 1 and X ₂ each independently represent an anionic group attached to the metal atom M or may be. chemically bonded to each other to form a ring having 4 to 7 atoms other than hydrogen, and the ring also contains a metal atom M. 2. The metallocene compound of the formula I in which the groups X, _X and X ₂ are selected from the group consisting of chloride, methyl, ethyl, butyl, isopropyl, isoamyl, octyl, decyl, benzyl, allyl, methylallyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, phenyl, toluyl, methoxy, ethoxy, isobutoxy, sec-butoxy, ethylsulfide, acetate. a propionate group, a group, a versatate butyrate group, a pivalate naphthenate group, a diethylamide group, a dibutylamide group, a bis (trimethylsilyl) amide group, bonded to form divalent or are anionic cross-groups such as trimethylene oxide or tetramethylene. 3. Compounds of formula Ia: Compounds of formula Ia according to claim 3 selected from the group consisting of: 5. A process for the preparation of compounds of formula Ia, which is carried out according to the following reaction scheme: and includes the following steps: (a) contacting 1-indanol derivatives of the formula II wherein the substituents R, _X and _R2 are as defined above, with LiBu to give the double salt of formula III; (b) reacting the lithium double salt of formula III obtained in step (a) with electrophilic reagents, such as diethyl carbonate, to form a hydroxyester of formula IV; (c) conducting a dehydration reaction of the alcohol function of the hydroxy ester of formula IV obtained in step (b) in an acid medium to form an ester of formula V; (d) carrying out a reduction reaction of the ester of formula (e) V obtained in step (c) of formula VI; to produce alcohol i generating a bromination reaction of an alcohol of formula VI to form a bromine derivative of formula VII; (f) forming an indenylcyclopentadienyl derivative of formula (Ia) using a bromine derivative of formula (VII) obtained in step (e) as starting material and a lithium salt of cyclopentadienyl anions whose corresponding neutral derivative can be represented by formula (VIII): in which. R ₃ , R ₄ , R ₅ and R _{6 have} the same meanings as defined above. '' · I: A method according to claim 5, characterized in that the reaction described in step (a) is carried out in the presence of basic reagents in an organic solvent at temperatures of -30 ° C to +120 ° C; the reaction described in step (b) is carried out in the presence of a hydrocarbon and / or ether solvent or mixtures thereof at temperatures ranging from -100 ° C to +120 ° C; - the reaction in step (c) is carried out in the presence of a solvent and a strong acid such as hydrochloric acid, sulfuric acid, paratoluenesulfonic acid, or weaker dehydrating agents such as silica gel at temperatures ranging from -25 ° C to + 150 °; the reaction in step (d) is carried out in an organic solvent with various reagents, for example LiAlH ₄ , NaBH ₄ , NaH, MgH ₂ , LiBu, LiMe, MeMgCl, PhMgBr, ButMgCl, at temperatures, that move in the range from -70 ° C to +100 ° C; the reaction in step (e) takes place in organic solvent using a brominating agent; the reaction in step (f) takes place in solvent selected from aromatic and / or aliphatic hydrocarbons and ethers and / or mixtures thereof, at a temperature ranging from -80 ° C to +120 ° C and the cyclopentadienyl anion is obtained by reacting the corresponding neutral derivative of formula VIII with a reagent selected from from alkyls or hydrides of electropositive metals, Grignard reagents or the same alkali metals and alkaline earth metals or their alloys, in a solvent selected from aliphatic or aromatic hydrocarbons, ethers and / or mixtures thereof and at temperatures of range from which -80 ° C to +110 ° C. The method of claim 6, mark ú ú c i s' a because of reaction in step (A) takes place in hexane as solvent in presence butyllithium and at temperatures which ranges from 0 ° C to + 70 ° C; the reaction of step (b) is carried out in hexane as solvent at temperatures ranging from -70 ° C to +25 ° C; the reaction of step (c) is carried out in toluene as solvent and in the presence of paratoluenesulfonic acid at temperatures ranging from +50 ° C to + 110 ° C; the reaction in step (d) is carried out in ethyl ether as an organic solvent in the presence of LiAlH ₄ at temperatures ranging from -30 ° C to +25 ° C; the reaction in step (e) is carried out in methylene chloride as a solvent and using PBr ₃ as the brominating agent at temperatures ranging from -20 ° C to + 250 ^° C; the cyclopentadienyl anion of the reaction in step (f) is I '' get the reaction of indene or 4, 7-dimethylindene with butyllithium in hexane / THF mixtures at temperatures ranging from 0 ° C to + 60 ° C. Process according to claim 5, characterized in that step (f) is carried out by reacting the brominated product of the general formula VII with a suitable lithium enolate resulting in the formation of the indenylcyclopentadienyl products of the general formula XIII: RJL XIII, where: R 1 and R ₂ independently of each other may occupy any free position of the indene group; R1, R2, R71 R ₈ , R ₈ , R 10 and R 11 independently represent a hydrogen atom, a halogen atom, preferably a fluorine atom, a chlorine atom or a bromine atom, a linear or branched saturated or unsaturated cycloaliphatic or aromatic hydrocarbyl group having 1 to 2 carbon atoms or a hydrocarbyl group of 20 carbon atoms substituted by one or more halogen atoms or a hydrocarbyl group having 1 to 20 carbon atoms containing one or more heteroatoms from 14; to 16. groups of the Periodic Table of the Elements, preferably from a silicon atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, or wherein any two adjacent substituents R ₉ , R ₁₀ and R 11 _are bonded to form a saturated or unsaturated cyclic structure. up to 20 carbon atoms containing a cyclopentadienyl ring bond, said structure optionally containing one or more heteroatoms specified above; R ₁₂ independently represents a hydrogen atom, a linear or branched saturated or unsaturated cycloaliphatic or aromatic hydrocarbyl group having 1 to 20 carbon atoms or a hydrocarbyl group having 1 to 20 carbon atoms containing one or more heteroatoms from Group 14 to 16 of the Periodic Table of the Elements, preferably a silicon atom, an oxygen atom, a nitrogen atom, a sulfur atom, and a phosphorus atom; wherein said process is carried out according to the following Reaction Scheme 2: vrrr XL xr and includes the following steps: (g) reacting the cyclic ketone of formula IX, wherein the substituents R ₉ , R 10 and R 11, as defined above, with lithium amide to form a mixture of anions of formula Xa and anions of formula Xb; (h) reacting a mixture of anions of formula Xa and anions of formula Xb with a brominated product of formula VII, which is prepared as outlined above (Reaction Scheme 1); (i) reduction of the functional carbonyl group to an alcohol group with suitable reagents to give a derivative of the general formula XII, wherein R _{12 is} as defined above; and (1) dehydrating the derivative of formula XII obtained in step (i) to give the desired indenylcyclopentadienyl compound of formula XIII wherein R 1, R 2, R 7, R 8, R 9, R 10, R 11 and R 12 are as defined above. 9. An olefin polymerization catalyst comprising the following reaction product: (A) one or more metallocene compounds of formula I, free or deposited on inert solids; and (B) one or more compounds capable of forming a metallocene alkyl cation. Catalyst according to claim 9, characterized in that component (B) is an aluminoxane. Process for preparing a catalyst according to claim 9 and 10, characterized in that component (A) is contacted with component (B) at temperatures ranging from +20 ° C to +60 ° C. and for a time ranging from 10 s to 1 h in a hydrocarbon medium and in an amount that provides an atomic ratio between aluminum in aluminoxane and a transition metal M of from 10 to 10,000, and preferably from 100 to 5000. An olefin polymerization process comprising the polymerization reaction of one or more olefin monomers in the presence of a catalyst according to claim 10. Process according to claim 12, characterized in that olefin monomers, such as ethylene and propylene, are polymerized in the presence of a metallocene compound of the formula I and methylalumoxane as a cocatalyst. Process according to Claim 13, characterized in that olefin monomers, such as ethylene and propylene, are polymerized in the presence of a metallocene compound of the formula I, an aluminum alkyl and a suitable boron compound as a cocatalyst.